CN100389096C - Process for producing slow releasing silicon potassium compound fertilizer by potassium feldspar - Google Patents
Process for producing slow releasing silicon potassium compound fertilizer by potassium feldspar Download PDFInfo
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- CN100389096C CN100389096C CNB2005100221541A CN200510022154A CN100389096C CN 100389096 C CN100389096 C CN 100389096C CN B2005100221541 A CNB2005100221541 A CN B2005100221541A CN 200510022154 A CN200510022154 A CN 200510022154A CN 100389096 C CN100389096 C CN 100389096C
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Abstract
The present invention discloses a method for producing a slow-release composite silicon-potassium fertilizer by potash feldspar, which uses potash feldspar, dolomite or/and serpentine and coke as raw materials. The prepared raw materials are heated into the melting state to carry out the roasting reaction; slurry in the melting state after the roasting reaction is quenched to the temperature of the natural environment by a quenching agent to form grit-shaped semi-products, and then the semi-products are dried and milled into powder so the slow-release silicon-potassium composite fertilizer is produced. The silicon-potassium fertilizer produced by the method of the present invention has the effects of a potassium fertilizer and a silicon fertilizer. The silicon-potassium fertilizer can be applied in lieu of the potassium fertilizer. The silicon-potassium fertilizer solves the problem of long time of serious fertilization disproportion of a nitrogen fertilizer, a phosphorus fertilizer and the potassium fertilizer due to low application rate of the potassium fertilizer. The silicon-potassium fertilizer can be directly applied and can be used as a coating of a quick-acting fertilizer. The production method of the slow-release composite silicon-potassium fertilizer disclosed by the present invention has the advantages of rich storage capacity and low price of raw materials for production, short process flow, low investment, convenient scaled production, etc.
Description
One, technical field
The present invention relates to a kind of production method of silicon potassium compound fertilizer, more particularly, relating to a kind of is the production method of raw material production silicon potassium compound fertilizer with the first feldspar.
Two, background technology
Plant growth mainly needs 16 kinds of essential nutritive elements, and with regard to importance, wherein potassium element occupies the 3rd.In the Chinese agriculture fertilising, nitrogen (N), phosphorus (P), potassium (K) ratio long-run disturbance are lower than reasonable levels, and especially potash fertilizer is out of proportion even more serious.Trace it to its cause, be since China can be directly used in the Potash Resources of producing potash fertilizer less, can not carry out a large amount of potash fertilizer production, have to from external a large amount of imports.With 1991 be example, only 12.7 ten thousand tons in potash fertilizer is produced in the whole nation per year, can not satisfy the needs of agricultural development far away, import potash fertilizer is up to 3,090,000 tons then.Therefore, searching can be used to produce the potassium resource of potash fertilizer, seeks new potash fertilizer production method, to satisfy the needs of agriculture production, to promoting that agricultural development has important practical significance.
Though it is few that China can be directly used in the water-soluble potassium ore resources of producing potash fertilizer, insoluble potassium ore resources is very abundant, of a great variety.Potassium felspar sand is exactly wherein more important a kind of.Usually people are potassium felspar sand with potash feldspar and microline.Their chemical constitution is identical, has not only contained potassium but also siliceous, and chemical formula is K
2O.Al
2O
3.6SiO
2, contain K
2O16.9%, Al
2O
318.4%, SiO
264.7%.Although the content of potassium oxide is not very too high in the potassium felspar sand, because of it is the most general a kind of rock, reserves are big in the earth's crust, and it is wide to distribute, and is many main ingredients that contain potassium silicate.These potassium ore resources if can be used to produce potash fertilizer, just overcome potash fertilizer resources of production problem of shortage, but mass production potash fertilizer promotes that to China agricultural produce will produce immeasurable effect.
Potassium felspar sand has very stable Si-Al-O network structure, and the chemical property stabilizer pole except that hydrofluoric acid, is decomposed by acid, alkali under the normal temperature and pressure hardly.Prior art thinks that low-temperature decomposing of potassium feldspar must be made auxiliary agent with fluorine-containing material, otherwise must carry out roasting at the high temperature more than 1800 ℃, changes its structure, improves its reactive behavior and could decompose.The researcher in this field is to be that the method for raw material production potash fertilizer has carried out inquiring into the potassium felspar sand many-sidedly, and main method has following several:
1, direct method.Potassium felspar sand, Wingdale and coal (as fuel) are ground into powder by a certain percentage, add the laggard capable high-temperature roasting of less water mixing balling-up, utilize calcium oxide to destroy the structure of potassium felspar sand mineral, pulverize again, be potash-lime fertilizer.The batching roasting can be carried out in shaft kiln or common kiln, also can carry out in mechanical vertical kiln.It is low that this method is carried the potassium cost, is still insolublely but enter element silicon in the fertilizer, still fails to obtain to utilize as the element silicon of crop alimentary component, so fertilizer efficiency is lower, prepared fertilizer is not silicon potassium compound fertilizer, more is not slow releasing silicon potassium compound fertilizer yet.
2, volatilization method.With other raw materials calcination at high temperature such as potassium felspar sand and Wingdales, the potassium volatilization is overflowed, captured recovery then, prepare the higher fertilizer of potassium content then.In order to solve the problem of utilizing of a large amount of residues, and the cost of reduction potash fertilizer, ideal method is in manufacture of cement, employing potassium felspar sand or other contain the clay in the potassium silicate rock place of cement batching, to improve the content of potassium in the cement ingredient, obtain the higher kiln ash potash fertilizer of potassium content.The potash fertilizer that adopts this method to produce, element silicon are still with insoluble component and enter in the fertilizer, and the fertilizer of gained is not silicon potassium compound fertilizer equally, also more are not slow releasing silicon potassium compound fertilizers.
3, leaching method
Under certain temperature and pressure, ore is handled, made potassium in the ore change the material of solubility into, make it leach out then, make potash fertilizer such as the higher Repone K of purity, vitriolate of tartar with acid, alkali or salt etc.The leaching method mainly contains salt method, lime burning method, acid system and alkaline process.
(1) salt method.Its basic technology is, the levigate balling-up of preparing burden of salt and potassium felspar sand is carried out roasting in 900 ℃ in shaft furnace, salt is heated to molten state, makes the salt of molten and potassium felspar sand carry out liquid and solid phase reaction.Because excessive fusion salt exists, the sodium in the salt cements out the potassium in the potassium felspar sand, generates to receive feldspar and Repone K, and water logging is after separate and can make the Repone K product.
(2) lime burning method.The basic technology of this method is, Wingdale and the levigate balling-up in back of potassium felspar sand batching are fuel with oil, and at the revolution roasting in kilns, temperature is 1300 ℃.Grog main component after the roasting is Dicalcium Phosphate (Feed Grade) and soluble potassium aluminate.Water leaching that grog is levigate, part potassium aluminate and water generate potassium hydroxide and aluminum hydroxide precipitation.After the filtration washing slagging-off, in filtrate, feed CO
2, carry out the carburizing reagent first time, generate salt of wormwood, aluminium hydroxide and lime carbonate etc., once filtering, filtrate 116 ℃ of following evaporation concentration to K
2CO
3Content is 40%-50%, cooling then, the thick potash fertilizer of elimination.Filtrate to gained feeds CO
2Carry out the secondary carbonization, generate KHCO
3Crystal separates obtaining KHCO
3Crystal grain then 400 ℃ of following calcinations, promptly obtains purity and can reach 90% above K
2CO
3
(3) acid decomposition.Basic skills is under 100 ℃ condition potassium felspar sand to be decomposed preparation potassium-ammonium sulfate binary compound fertilizer, by-product poly aluminium chloride, white carbon black with sulfuric acid and auxiliary agent.
(4) caustic leaching process.Prior art is less to this processing method research, and Japan once adopted the method for the quick decomposing of potassium feldspar of High Temperature High Pressure, promptly uses NaOH-Ca (OH) under 100～400 ℃ condition
2Mixed solution high pressure extraction potassium ion is produced potash fertilizer through further processing.The leaching yield of potassium is more than 90%, and the percentage extraction of silicon is below 2%.
Above-mentioned is the various leaching methods that raw material is produced potash fertilizer with the potassium felspar sand, the potash fertilizer products of being produced, no matter be Repone K or salt of wormwood, or potassium-ammonium sulfate, equally do not belong to silicon potassium compound fertilizer, more be not slow releasing silicon potassium compound fertilizer, the silicon components in the potassium felspar sand does not still obtain reasonable use yet.
Siliceous fertilizer is a kind of to contain the solubility in citric acid mineral manure of Calucium Silicate powder, has features such as nonpoisonous and tasteless nothing corrosion and difficult loss, is the required important nutritive element of plant.Experimental study shows that siliceous fertilizer all has important effect to the growth of farm crop such as paddy rice, wheat, corn, cotton, peanut, soybean, oil honor, sugarcane, potato class, fruit tree.In China, be that a lot of geographic soil lack silicon on the one hand, as the scarce silicon of the soil of the Yangtze valley 70%, the Yellow River and Huai He River sea region and Liaoning have the soil of half to lack silicon approximately, and the zone that lacks silicon is also progressively enlarging.Be that people are not enough to the effect understanding of siliceous fertilizer in crop growth on the other hand, the throughput less investment of siliceous fertilizer yields poorly, siliceous fertilizer is not added in the farmland substantially for many years, growth to farm crop is very unfavorable, and particularly the serious acid soil that lacks silicon in south is very unfavorable to the growth of paddy rice.And the production of siliceous fertilizer is in the ground zero stage in China, is mostly at present to utilize to have the active scrap silicon production that contains, as yellow phosphorus slag, waste steel slag.Siliceous fertilizer with these raw material production is single siliceous fertilizer, and solubility is not high, and fertilizer efficiency is also lower.
What of the volume increase of farm crop and rate of fertilizer application are relevant, but the fertilizer nutrition composition that more from fertilizer, effectively absorbs with farm crop what are relevant.After the azophoska that prior art provides is used, effective specific absorption of farm crop is all lower, average utilization as nitrogen in the nitrogenous fertilizer only is 35%, with rainwater run off and escape into air reach 45%, what be fixed in soil accounts for 20%, the practical efficiency of phosphate fertilizer and potash fertilizer is lower, generally has only 20%.Best fertilization mode is the feeder capability according to crop fertilizer requirement and soil, the various nutritive elements that repeatedly a spot of additional plant growth is required.The ideal way is to produce a kind of fertilizer that can directly impose on crop rhizosphere, and can regulate its nutrient releasing speed according to the different needs amount of plant growth time.May command that Here it is discharges fertilizer, is called for short controlled release fertilizer (CRF).Controllable release fertilizer is the advanced subject in the current fertilizer research.For the research of may command release fertilizer, states such as Japan, the U.S., Europe, Israel and Korea S have done a large amount of work.It is the urea of coating that Japan has developed with synthetics, the release rate of may command nitrogen, and nitrogen only discharged 80% in 100 days, and the utilization ratio of nitrogen can reach 83.2%.Be mainly used in fertilization of rice.The controlled release fertilizer of the U.S., Europe, Japanese Development and Production, do the coating except adopting materials such as polymkeric substance, paraffin wax, sulfide, also Development and Production goes out the compound with slow-releasing or microsolubility, as the controlled release fertilizer of materials such as urine aldehyde cpd, magnesium ammonium phosphate, oxamyl as coating.In national music happiness execute the divalent metal ammonium phosphate sylvite coated urea that popularization center of the multiple fertilizer technology institute of phosphorus releases, the formed nano level duct of covering accounts for more than 90%, can prolong fertilizer efficiency action time greatly, release period can reach 90～120 days.But it itself is exactly a kind of various plants nutrition composition that contains that prior art is not also developed, and except that can directly using, can be used as the slowly-releasing comprehensive silicon potash fertilizer of quick-acting nitrogen fertilizer slow-releasing coatings such as urea again.
Three, summary of the invention:
The potassium ore resources shortage of the solubility of the be directly used in production potash fertilizer that exists at the fertilizer production technology field, the demand of potash fertilizer soil big and vast region need replenish silicon, and the output of siliceous fertilizer is low, the object of the invention provides that a kind of very abundant and very cheap again potassium felspar sand is a raw material with reserves, be converted into the solubility in citric acid composition by the insoluble potassium that it is contained, silicon composition, in soil, can slowly discharge, have the silicon potassium compound fertilizer preparation method of higher utilization rate of fertilizer.Slow releasing silicon potassium compound fertilizer by method preparation of the present invention promptly can be used as a kind of compound manure of directly using, and also can be further used as the controlled coating agent of other quick-acting chemical fertilizer.
Main thought of the present invention is the composition according to potassium felspar sand, by adding suitable additive, the chemical bond of potassium felspar sand is disintegrated, cooling is handled through quenching, form the amorphous glass body, make its contained silicon, potassium composition change Chinese holly fusibleness silicon potassium stripping body into, change slow-release fertilizer into.The compound manure of gained can make system be in metastable state, can progressively discharge under certain edaphic condition again.
Realizing the concrete technical scheme of foregoing invention purpose of the present invention, is the method for raw material production slow releasing silicon potassium compound fertilizer with the potassium felspar sand promptly, mainly comprises following processing step:
1, batching: with potassium felspar sand, rhombspar or/and serpentine, coke prepare burden by 1: 0.5～3.8: 2.0～3.0 ratio of weight and number.
2, roasting: the raw material that proportioning is good is heated to molten and carries out roasting reaction, 1200～1560 ℃ of roasting temperature of reaction, 0.5～3.0 hour roasting reaction times.The height of maturing temperature is relevant with the concrete composition of raw material with the length of time, because of the composition of raw material different different.Maturing temperature should be able to make raw materials melt, and the time of roasting should be able to guarantee the roasting sufficient reacting.
3, quenching: the reacted molten state slip of roasting is carried out quenching with quenching medium, make it be cooled to the physical environment temperature, form the work in-process of sand shape;
4, grinding: the work in-process grinding of sand shape to powder, is promptly made slow releasing silicon potassium compound fertilizer.
In above-mentioned method with potassium felspar sand production slow releasing silicon potassium compound fertilizer, batching except containing first feldspar, rhombspar or/and serpentine raw material and the coke that acts as a fuel, in batching, also can add parts by weight and be 0.5～3.0 phosphorous mineral aggregate,, make Si-K fertilizer contain phosphorus magnesium component simultaneously as gypsum.In order to improve fertilizer efficiency, adapt to different soil, also can form the requirement of component according to the product slow releasing silicon potassium compound fertilizer, in batching, add other raw mineral materials, to increase the nutrient kind of compound manure.
In above-mentioned method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand, the molten state slip is carried out the quenching medium of quenching, can be water, air or water and AIR MIXTURES.When quenching medium is selected water or water and AIR MIXTURES, carry out drying earlier before the sand shape semi-product material conducting powder mill, remove moisture, so that carry out grinding processing better.
In above-mentioned method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand, or/and serpentine, and other raw mineral materialss that add in order to increase fertilizer nutrient component kind must become be of a size of 5～30mm through the worker as the potassium felspar sand of proportion material, rhombspar.Coke is of a size of 10～60mm.The finished product slow releasing silicon potassium compound fertilizer that has the sand shape work in-process to grind, wherein the particle diameter part that is not more than 0.18mm is no less than 90%.
Disclosed by the invention is the method for raw material production slow releasing silicon potassium compound fertilizer with the potassium felspar sand, component rhombspar in its batching is or/and serpentine is a kind of promotor, it is again a kind of fusing assistant, rhombspar is or/and the adding of serpentine, both can in high-temperature calcination process, promote potassium felspar sand chemistry key to disintegrate, reduce the chemical stability of potassium felspar sand, its insoluble potassium component and silicon components are transformed under certain edaphic condition, are the component of solubility, can reduce the maturing temperature of potassium felspar sand again, can fusion under 1200 ℃ of temperature, reduce greatly than the maturing temperature of 1800 ℃ of prior aries.The distinctive quenching technology of the present invention for both having destroyed original lattice, can make system be in metastable Chinese holly fusibleness silicon potassium stripping body again molten state potassium felspar sand quenching, changes the slow-release fertilizer that can progressively discharge fertilizer efficiency under the acid soil condition into.The silicon potassium compound fertilizer that adopts method of the present invention to produce is a kind of long-acting silicon potassium compound fertilizer, and can satisfy the needs of farm crop by adding the sustained-release long-acting compound fertilizer that other fertilizer nutritive element production has multiple fertilizer nutritive ingredient to multiple fertilizer nutritive ingredient.
In nitrogen, phosphorus, three kinds of fertilizer of potassium, the potash fertilizer of China is the most in short supply, and breach is more than 80%.Si-K fertilizer is the good no chlorine fertilizer of a kind of fertilizer efficiency, can substitute a part of potash fertilizer, and the mass production of Si-K fertilizer can solve the potash fertilizer problem of shortage.Of the present invention open, opened up the very abundant and cheap raw material resources-potassium felspar sand of a kind of reserves for the production of silicon potassium compound fertilizer, fundamentally solved the insufficient problem of production Si-K fertilizer raw material resources.Obtained solution owing to produce the raw material of Si-K fertilizer, thereby can produce by the great amount of investment Si-K fertilizer, improve the throughput of silicon potassium compound fertilizer, thereby solved potash fertilizer, siliceous fertilizer yields poorly, nitrogen, phosphorus, potash fertilizer Application Ratio are seriously lacked of proper care, vast scarce tripoli ground can not get element silicon for a long time and replenishes, have a strong impact on agricultural produce etc. problem.Because element silicon is the indispensable nutritive elements of high-quality farm crop, thereby also can effectively promote high-quality and efficient Agricultural Development.If the present invention obtains promotion and implementation, both can realize adjusting the fertilizer variety structure, can satisfy " mending the potassium engineering " that agrosystem carries out demand again to potash fertilizer.Enforcement of the present invention, except the investment new production line, can be on the basis of existing equipmenies such as cement mill, Steel Plant and phosphate fertilizer plant, can produce slow releasing silicon potassium compound fertilizer by adjusting slightly to transform, changing the line of production for cement mill, Steel Plant and phosphate fertilizer plant etc. provides new way, has favorable economic benefit.
It is short that the slowly-releasing comprehensive silicon potash fertilizer production method that the present invention discloses has technical process; reduced investment; and be convenient to advantages such as large-scale production; a kind of durable composite fertilizer on the slowly-releasing comprehensive silicon potash fertilizer of producing; under the acid soil condition, can slowly discharge fertilizer efficiency; except that can also can be used as the coating agent of quick-acting chemical fertilizer directly as using the fertilizer.
Four, description of drawings:
Accompanying drawing 1 is the process flow sheet of an example of the present invention.
Five, embodiment
Embodiment 1
With the method that potassium felspar sand is produced slowly-releasing comprehensive silicon potash fertilizer, the technical process of present embodiment as shown in Figure 1.Potassium felspar sand, rhombspar ore be crushed to be of a size of 15～30mm, coke is crushed to and is of a size of 30～60mm, and then in potassium felspar sand: rhombspar: the parts by weight ratio of coke=1: 1.2: 2.4 is prepared burden in feed bin.The ingredients by weight umber ratio of present embodiment potassium felspar sand, rhombspar, coke all can in 1: 0.6～2.0: 2.0～2.8 scope.Confected materials is added high temperature reaction stove carry out roasting, maturing temperature is controlled at (1250～1450 ℃ scopes) about 1300 ℃, about about 1 hour of roasting time.After roasting finishes, the molten state slip is carried out quenching with water slug, be cooled to envrionment temperature, form the sand shape work in-process, after the drying, be ground into 90% powder that is not more than 0.18mm (being not less than 80 orders), promptly be prepared into the product slow releasing silicon potassium compound fertilizer.
Embodiment 2
With the method that potassium felspar sand is produced slowly-releasing comprehensive silicon potash fertilizer, the present embodiment technical process has just been lacked dry workshop section wherein substantially as shown in Figure 1.Potassium felspar sand, rhombspar, serpentine ore be crushed to be of a size of 5～15mm, coke is crushed to and is of a size of 10～30mm, and then in potassium felspar sand: rhombspar: serpentine: coke=1: 0.6: 0.8: 2.5 parts by weight ratio is prepared burden in feed bin.The ingredients by weight umber ratio of present embodiment potassium felspar sand, rhombspar, serpentine, coke all can in 1: 0.4～1.2: 0.6～1.0: 2.2～3.0 scope.Confected materials is added high temperature reaction stove carry out roasting, maturing temperature is controlled at (1250～1450 ℃ scopes) about 1400 ℃, about about 1.5 hours of roasting time.After roasting finishes, the molten state slip is disperseed to carry out quenching with air-flow, be cooled to envrionment temperature, form the sand shape work in-process, be ground into 90% powder that is not more than 0.18mm (being not less than 80 orders) then, promptly be prepared into the product slow releasing silicon potassium compound fertilizer.
Embodiment 3
With the method that potassium felspar sand is produced slowly-releasing comprehensive silicon potash fertilizer, the technical process of present embodiment as shown in Figure 1, and is substantially the same manner as Example 1.Potassium felspar sand, rhombspar, serpentine, gypsum ore be crushed to be of a size of 15～20mm, coke is crushed to and is of a size of 30～50mm, and then in potassium felspar sand: rhombspar: serpentine: gypsum: coke=1: 1.6: 1.8: 1.0: 2.6 parts by weight ratio is prepared burden in feed bin.The ingredients by weight umber ratio of present embodiment potassium felspar sand, rhombspar, serpentine, gypsum, coke all can in 1: 1.0～1.6: 1.6～2.2: 0.5～2.6: 2.0～2.6 scope.Confected materials is added high temperature reaction stove carry out roasting, maturing temperature is controlled at (1350～1550 ℃ scopes) about 1550 ℃, about about 2.5 hours of roasting time.After roasting finishes, the molten state slip united with G﹠W disperse to carry out quenching, be cooled to envrionment temperature, form the sand shape work in-process, after the drying, be ground into 90% powder that is not more than 0.18mm (being not less than 80 orders), promptly be prepared into the product slow releasing silicon potassium compound fertilizer.
Claims (7)
1. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand is characterized in that mainly comprising following processing step:
(1) batching: with potassium felspar sand, rhombspar or/and serpentine, coke prepare burden by 1: 0.5～3.8: 2.0～3.0 ratio of weight and number;
(2) roasting: the raw material that proportioning is good is heated to molten and carries out the roasting reaction, and the roasting temperature of reaction is 1200～1560 ℃, and the roasting reaction times is 0.5～3.0 hour;
(3) quenching: the reacted molten state slip of roasting is carried out quenching with quenching medium, make it be cooled to the physical environment temperature, form the work in-process of sand shape;
(4) grinding: sand shape work in-process grinding to powder, is promptly made slow releasing silicon potassium compound fertilizer.
2. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 1 adds also in it is characterized in that preparing burden that parts by weight are arranged is 0.5～3.0 phosphorous mineral aggregate.
3. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 1 and 2 is characterized in that said quenching medium is water, air or water and AIR MIXTURES.
4. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 3 is characterized in that when quenching medium is water or water and AIR MIXTURES, carries out drying before the material grinding earlier.
5. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 1 and 2 is characterized in that said potassium felspar sand, rhombspar are or/and the serpentine raw materials size is 5～30mm.
6. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 1 and 2 is characterized in that said coke raw materials size is 10～60mm.
7. method of producing slow releasing silicon potassium compound fertilizer with potassium felspar sand according to claim 1 and 2 is characterized in that said grains of sand shape work in-process grinding to the part that particle diameter is not more than 0.18mm is no less than 90% powder.
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| CN1084842A (en) * | 1992-09-28 | 1994-04-06 | 贵州大学 | A kind of novel method of producing potash-lime fertilizer |
| CN1456538A (en) * | 2003-06-06 | 2003-11-19 | 马文波 | Potassic-magnesian fertilizer and preparing method thereof |
| CN1493548A (en) * | 2003-09-11 | 2004-05-05 | 汪敬恒 | Granular chlorine less potassium calcium silicon magnesium fertilizer and its manufacturing method |
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| CN1793065A (en) | 2006-06-28 |
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